EIS measurements for the

Electrochemistry in Historical and Archaeological Conservation

performance evaluation of organo-

Workshop January 11 - 15 2010, Leiden, The Netherlands

silane in the protection of outdoor

monumental bronzes
P. Letardi
CNR - ISMAR, Genoa, Italy

E.Joseph, S.Prati, R.Mazzeo

University of Bologna, M2ADL Laboratory, Ravenna,
Italy

Eu-ARTECH EC Integrated Infrastructure initiatives

Access, Research and Technology for the 6th Framework Program –
conservation of the European Cultural Heritage Structuring the European Research Area
 Eu-ARTECH EC Integrated Infrastructure initiatives
Access, Research and Technology for the 6th Framework Program –
Structuring the European Research Area
Electrochemistry in Historical and Archaeological Conservation

conservation of the European Cultural Heritage

JOINT RESEARCH ACTIVITY 1

Workshop January 11 - 15 2010, Leiden, The Netherlands

Development and evaluation of new treatments for the conservation-

restoration of outdoor bronze monuments

Task 1:IDENTIFICATION, SELECTION AND

CHARACTERIZATION OF BRONZE SAMPLES Eddy current thickness
FOR TESTING
measurements

Task 2: LABORATORY STUDIES ON NEW

TREATMENTS

Task 3:AGEING PROCEDURES AND

Colour measurements
CHARACTERISTICS OF SAMPLES PROPERLY
AGED BEFORE TREATMENTS

Task 4: TREATED SAMPLES, EXPOSURE EIS measurements

SITES AND AGEING PROCEDURES

Task 5: PERFORMANCE OF THE

TREATMENTS DURING NATURAL AND FTIR microspectroscopy
ARTIFICIAL AGEING PROCEDURES

Task 6:IN SITU TESTS OF TREATMENTS ON

OLD ARTIFACTS (DEMO ACTIVITY) X-ray diffraction
 TYPOLOGIES OF TREATMENTS SELECTED
Electrochemistry in Historical and Archaeological Conservation
Workshop January 11 - 15 2010, Leiden, The Netherlands

Acrylic lacquers (Incralac), various waxes (wax R21, TeCe Wachs 3534F) and organic
corrosion inhibitors (benzotriazole) are the most frequently used treatments for outdoor
bronze protection. In order to response to the pressing need voiced by art conservators, this
project aimed at evaluating new approaches based on alternative materials for the protection
of outdoor bronze monuments as well as new inhibition treatments for active corrosion.
Different typologies of treatments were selected:

1. New generation of silanes, which are

commonly applied to protect stone
monument, were chosen for their ability
to produce, after hydrolysis, chemical
bonds with copper hydroxysulphates or
hydroxychlorides.
treatme name Type of functional
nt group Rf
T1 dynasylan
2. formation of artificial copper oxalate patinas F8263
- (CF2)5CF3

3. formation of artificial copper oxalate by fungi T2 SIVO clear ® (?)

4. formation of a thicker cuprite layer T3 protectosil SC ® (?)

5. limewater as corrosion inhibitor T4 dynasylan BSM

40
-CH(CH3)OCH3
 EIS: Instruments and methods
Electrochemistry in Historical and Archaeological Conservation
Workshop January 11 - 15 2010, Leiden, The Netherlands

WE REF CE

Potentiostat
E I 
FRA

Electrolyte
Personal
Computer

•All the EIS spectra have been acquired with the same
contact probe setup developed to make measurements on
art object also
Letardi P., Laboratory and field test on patinas and protective coating systems for outdoor bronze monuments, in: Ashton J.,
Hallam D.(Eds.), Proceedings of Metal2004, National Museum of Australia, Canberra, 2004, pp. 379-387

http://www.nma.gov.au/shared/libraries/attachments/publications/metal_04_proceedings/section_3_better_understanding_of
_treatments/files/7852/NMA_metals_s3_p12_patinas_protective_coating.pdf
 EIS: Instruments and methods
Electrochemistry in Historical and Archaeological Conservation
Workshop January 11 - 15 2010, Leiden, The Netherlands

The measurement area is 1.767 cm2. A commercial cleaning-cloth soaked with

a mineral water (electrical conductivity 320mS/cm, pH=7.9) is fixed to the
contact cell, and the system obtained is then leant on the surface to be
measured. The cloth has been immersed in the mineral water for 120min
before being fixed to the contact cell. The EIS spectra acquisition has been
started after a time to around 30min after the cell is leant on the measurement
area, in order to stabilise the open circuit potential.

•Transportable instrumentation has been used

•Gamry FAS1 Femtostat
•Measurements conditions:
•frequency range: 100Khz-10mHz
•applied potential: 10 mVrms
•acquisition: 10 points/decade
•EIS spectra acquisition time  20-45min
 PRELIMINARY EVALUATION OF TREATMENTS
Electrochemistry in Historical and Archaeological Conservation

Treatments
Workshop January 11 - 15 2010, Leiden, The Netherlands

UN samples T1
Dynasylan F8263
1) Microcrystalline wax R21 + treatment
2) treatment T2
SIVO clear
3) reference without treatment
T3a
Protectosil SC
T3b
Protectosil SC
T3c
Protectosil SC

Colleoni bronze monument (Andrea del Verrocchio 1476) T3d

Protectosil SC
sceptre T4
Dynasylan BSM 40
T5
VP 5035
T1 T2 T3bT4 T5 T3c T6 T9 T6
Incralac
123 12 3….
T7
Microcrystalline wax R21
length 1m, Ø 6 cm
T9
Wax TeCe 3534F
Joseph E., Letardi P., Mazzeo R., Prati S., Vandini M., Innovative treatments for the protection of outdoor bronze
monuments, in: C.Degrigny, R. van Langh, I. Joosten, B.Ankersmit (Eds.), Proceedings of Metal07, Amsterdam 2007, v5 pp.
71-77
 PRELIMINARY EVALUATION OF TREATMENTS
Electrochemistry in Historical and Archaeological Conservation
Workshop January 11 - 15 2010, Leiden, The Netherlands

Treatments
T1
Dynasylan F8263
T2
SIVO clear
T3a
Protectosil SC
T3b
Protectosil SC
T3c
Protectosil SC
T3d
Protectosil SC
T4
Dynasylan BSM 40
All treatments have been documented and analysed with the use of colorimetry,
T5
thickness measurements, corrosion tests (EIS), FTIR microscopy and cross-sections
VP 5035
analysis with optical microscopy and SEM-EDX, after 8 months weathering in Venice.
T6
Incralac
• The EIS analyses performed showed that just T1 and T2 silanes
presented a resistance to corrosion comparable to the treated with Incralac T7
coupons. Microcrystalline wax
R21
• The advantage of causing any colour modification to the untreated patina T9
was also used as a selection factor and highlighted with colorimetric Wax TeCe 3534F
measurements.
 BRONZE SAMPLES FOR TESTING
Electrochemistry in Historical and Archaeological Conservation
Workshop January 11 - 15 2010, Leiden, The Netherlands

The EU-ARTECH partners decided to use the Rg5

alloy (85% copper, 5% tin, 5% zinc, 5% lead bronze, UN
G-CuSn5ZnPb according to DIN 1705).
Bronze alloy samples, of size 70 mm x 50 mm x 2,5
mm and average weight of 85 g, have been
obtained from polished single cast alloy sheets of
400 mm x 300 mm

UA MN

A set of copper roof (UN = R)

The set of “urban artificial” (UA) was
sent by BLfD to Prof. Pichler,
Hochschule für Angewandte Kunst,
Vienna, in order to produce his
patented cuprite / brochantite
surface layer. A preliminary
chemical analysis has confirmed the
presence of cuprite and brochantite
were made available by
Bayerisches Landesamt für
Denkmalpflege (BLfD). They
were naturally aged for 80
years on the roof of the BLfD
To obtain a natural marine patina on premises.
the bronze specimens (MN) it was
decided to expose the bronze
specimens at the Cabo Raso (P)
exposure test site, according to EN
ISO 8565. The angle of exposure is
30º and the exposure racks are facing
the sea direction. The Mn samples
have been exposed one year.
 BRONZE SAMPLES FOR TESTING
Electrochemistry in Historical and Archaeological Conservation

Distribution |Z| on Patinas

Workshop January 11 - 15 2010, Leiden, The Netherlands

10mHz

100

UN
UN

|Z| 10mHz [KW ]

UN MN UA
UA
◊ Natural ◊ Natural
UA
◊ Artificial
◊ 80 years ◊ 1 year ◊ Pichler
urban marine process 10
◊ 20 µm ◊ 30 µm ◊ 80 µm
◊ brochantite ◊ Atacamite ◊ brochantite MN
M
|Z|10mHz = 69 ± 18 KW |Z|10mHz = 5 ± 2 KW |Z|10mHz = 29 ± 4 KW
N
For each patina under examination, five to twenty-two
spectra have been measured in different sample areas
and on several coupons, in order to check homogeneity
and repeatability of results 1
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
Sample

According to the EIS measurements, the patinas under investigation show impedance
values on a wide range.
The wide dispersion of data obtained suggests a poor homogeneity of samples, especially
for MN and UN patinas.
 EIS data before weathering
Electrochemistry in Historical and Archaeological Conservation

The dishomogeneity of samples would require

Workshop January 11 - 15 2010, Leiden, The Netherlands

a large number of measurements in order to

properly statistically evaluate the results.
Nonetheless, due to the large number of
patina/coating combinations under study, a
compromise was necessary in order to keep
the measurement time affordable. For each
combination, both measurements on different
coupons of the same kind and repeated
measurements on different area of the same
coupon have been considered; whenever
possible, a larger number of measurements
has been performed when larger dispersion of
data was obtained. Based on the number of
measurements available and their distribution,
average |Z|10mHz values computed as centre =
treatment Name typology
(Max value+min value)/2 and half range =
(Max value-min value)/2 appeared more
T1S Dynasylan F8263 organic-inorganic appropriate.
UN coupons with T1S and Tref coating have
T2S SIVO clear organic-inorganic
been measured after a first application
T3S Cuprite layer inorganic (October 2006); because of the unexpected low
impedance values measured, all samples with
Tref Incralac acrylic resin
T1S, T2S, Tref, I1S and Iref have been treated
I1S Limewater 0,5% passivation again (December 2006) and EIS
Iref Benzotriazole complex
measurements repeated in order to enlighten
the modifications.
 EIS data before weathering
Electrochemistry in Historical and Archaeological Conservation

• Before ageing procedures,

Workshop January 11 - 15 2010, Leiden, The Netherlands

Tref T1S T2S

M coating Tref provides a very
N 102 102 102
good protection on all patinas

|Z|10mHz [KW]
|Z|10mHz [KW]

|Z|10mHz [KW]
but for MN, where the protection
is poor; a very wide dispersion
101 101 101

of data is obtained and a very

critical behaviour on application,
coated coated coated
100 100 100
patina patina patina

as one order of magnitude

MN15

MN16

MN17

MN18

MN45

MN46
MN6

MN7

MN8
MN26

MN35

MN36

MN37

MN38

MN39

MN10

MN12

MN14
sample sample sample difference between |Z|10mHz
105 104 104 values after the first and second
UN Tref T1S T2S
application on UN coupons has
been obtained.
104 103 103
|Z|10mHz [KW]

|Z|10mHz [KW]

|Z|10mHz [KW]
103 102 102
•T1S and T2S coatings have
102 101 101
very similar behaviour; they
coated
patina
coated
patina coated provide in general a poor
protection.
coated (1) coated (1) patina
101 100 100
UN7

UN9
UN35

UN36

UN37

UN38

UN39

UN40

UN10

UN11

UN13

UN14

UN15

UN16

UN17

UN18

UN19

UN20
sample sample sample • Those results confirm that
105 105 105
attention should be paid to the
UA Tref T1S T2S patina/coating system, as the
104 104 104 same coating could provide
different performance on
|Z|10mHz [KW]

|Z|10mHz [KW]
|Z|10mHz [KW]

103 103 103

different patinas.
102 102 102
•Several outliers have been
101 101 101
found, which account for the
large variability of the systems
UA33

UA34

UA35

UA36

UA38

UA13

UA14

UA15

UA16

UA17

UA18
UA7

UA8

UA9

UA10

UA11

UA12

sample sample sample under investigation.

 EIS data before weathering
Electrochemistry in Historical and Archaeological Conservation
Workshop January 11 - 15 2010, Leiden, The Netherlands

Urban Natural
Urban Natural UN
UN Substrate
Substrate Marine natural
Marine natural MN
MN Substrate
Substrate Urban artificial
Urban artificial UA
UA Substrate
Substrate
1055
10 1055
10 1055
10
UNsubstrate
UN substrate MNsubstrate
MN substrate UAsubstrate
UA substrate
UNsubstate
UN substate(1)
(1)

1044
10 1044
10 1044
10
10mHz [KW]

1033

10mHz [KW]
1033

10mHz [KW]
[KW]

10 1033

[KW]
10 10

[KW]
10mHz
|Z|10mHz

|Z|10mHz
10mHz
|Z|10mHz
|Z|

|Z|
1022

|Z|
10 1022
10 1022
10

1011
10 1011
10 1011
10

1000
10 1000
10 1000
10
none Tref
none Tref T1S
T1S T2S
T2S T3S
T3S I1S
I1S Iref
Iref none Tref
Tref T1S
T1S T2S
T2S T3S
T3S I1S
I1S Iref
Iref none
none Tref
Tref T1S
T1S T2S
T2S T3S
T3S
none

Treatment
Treatment Treatment
Treatment Treatment
Treatment

Coating Tref provides a good protection on all patinas but for MN, where the protection is
poor; a very wide dispersion of data is obtained for this treatment. On UN substrate where
EIS data before first (1) and second treatment are available, a large difference is obtained.
T1S and T2S coatings have very similar behaviour; they provide in general a poor
protection. For T1S on UN substrate one can also notice the lower sensitivity to further
application with respect to Tref
 Natural weathering
Electrochemistry in Historical and Archaeological Conservation
Workshop January 11 - 15 2010, Leiden, The Netherlands

MN Comment / use For the ageing of conservation treatments applied to bronze

MN 06 specimens with marine natural (MN) patinas coupons were
MN 08 T1S exposed in the marine atmosphere test site Cabo Raso (P)
MN 10 for 18 months. The exposure site is the same that was used
MN 16
for the marine patina formation. The exposure started on
26th April 2007. A representative set of 3 samples has been
chosen for each treatment under evaluation. The climatic
MN 17 T2S

MN 18 data have been recorded from a closed meteorological

MN 22 station. The ageing in marine natural environment ended on
MN 23 T3S 27th October 2008.
MN 24

MN 36

MN 37 Tref

MN 38

MN 42

MN 43 I1S

MN 44

MN 52 MN UA UN (R) Set IV Set V Comment/use

MN 53 Iref
MN48 UA31 UN05 QQ11 QQ27
MN 54 Blank
MN50 UA32 UN06 QQ33
Different UN, UA, MN coupons were also exposed in the MN12 UA11 UN11 QQ39 QQ60
urban-marine atmosphere test site inside Genoa Harbour (I) T1S
for 18 months. The exposure started on 22nd May 2007. For MN14 UA12 UN14 QQ41

each typology of treatment, a set of 2-3 samples has been MN45 UA13 UN19 QQ42 QQ81
used. Nearby, a meteorological station has collected
T2S
MN46 UA14 UN20 QQ78
ongoing climatic data (temperature, relative humidity, MN20 UA20 UN25 T3S
pressure, precipitations, sunlight and Time of Wetness
ToW). The ageing procedure has ended on 3rd December MN26 UA33 UN39 QQ80 QQ88
Tref
2008. MN39 UA34 UN40 QQ90
 Artificial ageing
Electrochemistry in Historical and Archaeological Conservation
Workshop January 11 - 15 2010, Leiden, The Netherlands

UA UN (R) Comment / use Because the corrosion processes in urban natural

UA 08 UN 09 environment may be very slow, for the ageing
UA 09 UN 10 P T1S conservation treatments applied to bronze
UA 10 UN 13 specimens with urban natural (UN) and urban
UA 16 UN 16 P
artificial (UA) patinas, it was decided to also carry
out accelerated ageing in laboratory chambers to
simulate an urban exposure.
UA 17 UN 17 T2S

UA 18 UN 18

UA 22 UN 22
The procedure consist of two parts:
UA 23 UN 23 P T3S (I) UV radiation exposition to promote degradation of
UA 24 UN 24 treatments according to the standard EN ISO
UA 36 UN 36
11341 2004 – “Paints and varnishes. Artificial
weathering and exposure to artificial radiation.
Exposure to filtered xenon-arc radiation ”
UA 37 UN 37
Tref
UA 38 UN 38
Bo (II) a salt solution exposition in a salt fog chamber to
UN 42 promote corrosion, according to standard ISO
UN 43 I1S
9227 2006 – “Corrosion tests in artificial
atmospheres. Salt spray tests” and the sprayed
solution has the composition NaCl (0,5 g/L) +
UN 44

UN 52 (NH4)2SO4 (3,5 g/L).

The treated samples were exposed alternatively to the
UN 53 Iref

UN 54 P UV radiation and to the salt solution, for periods of

two weeks in each test cabinet, till having reached
a total of 2000 h of ageing. The artificial ageing of
the 24 samples started in February 2008 and
ended in July 2008.
A representative set of 3 samples has been chosen for
each treatment under evaluation as shown in
table 3.
 EIS data after 9months weathering
Electrochemistry in Historical and Archaeological Conservation
Workshop January 11 - 15 2010, Leiden, The Netherlands

• same setup used for measurements before exposure

• at least two measurements for each patina/coating system
 Treatments behaviour
Electrochemistry in Historical and Archaeological Conservation
Workshop January 11 - 15 2010, Leiden, The Netherlands

None 105
Tref T1S T2S
103 103 104
T1S 9 months
Patina 9 months T1S
Patina
104

102 102 103

|Z|10mHz[KW]
|Z|10mHz[KW]
|Z|10mHz[KW]
103
|Z|10mHz[KW]

102

101 101 102

101
Tref 9 months
T1S 9 months
Tref T1S
100 100 101
100
UN UA MN QQ IV QQ V UN UA MN QQ IV QQ V
UN UA MN QQ IV QQ V UN UA MN QQ IV QQ V
Substrate Substrate Substrate Substrate

• After the 9 months exposure in Genoa Harbour small differences on patina are
generally obtained
•Tref shows a marked impedance decrease on all substrate but for MN an
increase is obtained
• T1S and T2S show a stable behaviour on some substrates and a more or less
marked impedance increase on others
 EIS data after 18months weathering
Electrochemistry in Historical and Archaeological Conservation
Workshop January 11 - 15 2010, Leiden, The Netherlands

• same setup used for measurements before exposure

• at least two measurements for each patina/coating system
 EIS on MN samples
Electrochemistry in Historical and Archaeological Conservation

103
Workshop January 11 - 15 2010, Leiden, The Netherlands

Marine Natural MN Substrate Tref T1S

102 102
|Z|10mHz [KW
102

|Z|10mHz [KW]

|Z|10mHz [KW]
101 101 101

coated coated
100 100
patina
100
patina
MN 9m (G) coated 18m coated 18m
MN 18m (G)

MN26

MN35

MN36

MN37

MN38

MN39

MN6

MN7

MN8

MN10

MN12

MN14
MN 0m (G)
3
10-1
Blank T1S T2S T3S Tref I1S Iref sample sample

Treatment T2S T3S

|Z|10mHz [KW

102
102 102

|Z|10mHz [KW]
|Z|10mHz [KW]
101
101 101

100
coated coated
MN 18m (P) patina
patina
MN 0m (P) 100 100
coated 18m coated 18m
10-1

MN20

MN21

MN22

MN23

MN24
MN15

MN16

MN17

MN18

MN45

MN46
Blank T1S T2S T3S Tref I1S Iref
Treatment sample sample

Iref I1S
102 102

|Z|10mHz [KW]

|Z|10mHz [KW]
101 101

coated coated
patina patina

• patina EIS value slightly increase

100 100
coated 18m coated 18m

MN51

MN52

MN53

MN54

MN41

MN42

MN43

MN44
• after 18m exposure no treatment provides a
sample sample

significantly higher impedance with respect to

patina
 EIS on UN samples
Electrochemistry in Historical and Archaeological Conservation

105 105 104

Workshop January 11 - 15 2010, Leiden, The Netherlands

|Z|10mHz [KW UN 9m (G)

UN 17m (G)
UN 0m (P)
Urban Natural UN Substrate Tref T1S

104 103
104

|Z|10mHz [KW]

|Z|10mHz [KW]
103 102
103
102 101
coated
102 coated
patina
patina
coated 18m coated 18m
101 100

UN35

UN36

UN37

UN38

UN39

UN40

UN7

UN9

UN10

UN11

UN13

UN14
1051
UN 18m (P)
Blank
UN 0m (P) T1S T2S T3S Tref I1S Iref sample sample
104 104
Treatment T2S T3S
|Z|10mHz [KW

104
103 103

|Z|10mHz [KW]

|Z|10mHz [KW]
103
102 102

102
101 101
coated coated
patina patina
coated 18m coated 18m
101 100 100

UN15

UN16

UN17

UN18

UN19

UN20

UN21

UN22

UN23

UN24

UN25
Blank T1S T2S T3S Tref I1S Iref
Treatment sample sample
104 104
Iref I1S

103 103

• values on coupon exposed in Genoa are systematically lower than

|Z|10mHz [KW]

|Z|10mHz [KW]
the one measured on artificially weathered samples. 102 102

• patina EIS value after 18m is the same on artificially weathered 101 101
coated coated
samples, while it’s one third on Genoa exposed ones patina
coated 18m
patina
coated 18m
100 100

•Tref shows a decrease of two order of magnitude; after 18m

UN51

UN52

UN53

UN54

UN41

UN42

UN43

UN44
exposure the values are the same as on bare patina sample sample

• T1S and to a lower extent T2S are characterised by higher values

than the corresponding patina both in Genoa (natural Weathering)
and in Portugal (artificial weathering)
 EIS on UA samples
Electrochemistry in Historical and Archaeological Conservation
Workshop January 11 - 15 2010, Leiden, The Netherlands

105 104
Tref T1S coated
104
Urban Artificial UA Substrate coated 18m
|Z|10mHz [KW

104 103

|Z|10mHz [KW]

|Z|10mHz [KW]
103
103 102
coated
coated 18m
102
UA 9m (G) 102 101
UA 18m (G)
UA 0m (G)
101
101 100

UA33

UA34

UA35

UA36

UA38

UA7

UA8

UA9

UA10

UA11

UA12
Blank T1S T2S T3S Tref
Treatment sample sample
104 104

T2S
coated T3S coated
coated 18m coated 18m

103 103

|Z|10mHz [KW]

|Z|10mHz [KW]
102 102

101 101

100 100

UA13

UA14

UA15

UA16

UA17

UA18

UA20

UA21

UA22

UA23

UA24
sample sample

• patina EIS value decrease a little after the 18 months exposure in Genoa Harbour
• Tref continue to show an impedance decrease
• T1S shows an impedance value little greater than the bare patina one, with a marked decrease with
respect to the value measured after 9 month exposure
• T2S results the only protective treatment after 18 months exposure on UA substrate, with impedance
value more than one order of magnitude greater than the bare patina one
 IN SITU TESTS OF TREATMENTS
Electrochemistry in Historical and Archaeological Conservation

The Florence cathedral’s doors have been selected as an example of urban site.
Workshop January 11 - 15 2010, Leiden, The Netherlands

The different treatments have been applied on a delimited area of the door
closed to the campanile by a specialized restorer following the procedures
individuated during the first part of the project.
The patina composition has been ascertained by the use of microFTIR combined
with ATR and resulted to be constituted of linarite (PbCu(SO4)(OH)2) and
should react with the silane treatments. The results showed also the presence of
past restoration products (microcrystalline wax, vinylic resin), which have been
removed before the application of the selected treatments on the door. This
critical point should be further studied, in particular the influence of past
restorations interventions and how new treatments can be further applied on.
 EIS on Florence cathedral’s doors
Electrochemistry in Historical and Archaeological Conservation
Workshop January 11 - 15 2010, Leiden, The Netherlands

1000
|Z|lf [KW cm2]

none Tref T1S T2S S1

100
The same setup as for the measurements on coupons has
been used. |Z|lf EIS values measured on the untreated
cathedral’s door surface is quite high, compared to other
values measured on outdoor bronze monuments:
- MIII,MV: Quarto Monument (Genoa)
- C1A, C2A, C3A, C4A, C5A: Colleoni statue (Venice)
10
Letardi P., Luciano G., Survey of EIS measurements on copper and bronze patinas,

in: C.Degrigny, R. van Langh, I. Joosten, B.Ankersmit (Eds.), Metal07, v3 pp. 44-50
CBN

UN
MN
MIII

QQ IV
MV
C1A
C2A
C3A
C4A
C5A

QQ V
CS
BBA

UA

FD

Treatments produces just a very slight increase, more

Sample pronounced for Tref and T2S
 Conclusions
Electrochemistry in Historical and Archaeological Conservation
Workshop January 11 - 15 2010, Leiden, The Netherlands

• EIS has been used to characterise the bare samples with

their patina before and after silane application. EIS
measurements have been repeated after 9 and 18 months
exposure at ISMAR-GENOA (I) marine exposure site or
Cabo Raso one. As Incralac is a widely used treatment in
conservation, also coupons with that treatment have
been considered for comparison.
• It has been clearly demonstrated how untreated
corrosion patinas are different in term of intrinsic
protection capability, and this certainly affects both
treatment application procedures and performance.
• Based on XRD results and SEM-EDS observations and
analysis carried on the UN samples, could be assume
that silane is more protective in a sulphur contaminated
environment than in the presence of chlorides
• The organo-silanes have shown similar properties to the
reference treatment but with a major stability. Due to
their expected long lasting service life, the maintenance
costs may be reduced to the minimum, facing the
problem of decreasing funding allocated to this aspect.
Electrochemistry in Historical and Archaeological Conservation
Workshop January 11 - 15 2010, Leiden, The Netherlands

•
•
•
•

M. Nesi (restorer)
G.Morigi (restorer)
G.Gaggero (CNR-ICB)
G.Cutugno (CNR-ISMAR)
Acknowledgements